Meteorites and Interplanetary Dust Particles (IDPs) are supposed to originate from asteroids and comets, sampling the most primitive bodies in the Solar System. They contain abundant carbonaceous material. Some of this, mostly insoluble organic matter (IOM), likely originated in the protosolar molecular cloud, based on spectral properties and H and N isotope characteristics. Together with cometary material returned with the Stardust mission, these samples provide a benchmark for models aiming to understand organic chemistry in the interstellar medium, as well as for mechanisms that secured the survival of these fragile molecules during Solar System formation. The carrier molecules of the isotope anomalies are largely unknown, although amorphous carbonaceous spheres, so-called nanoglobules, have been identified as carriers. We are using Secondary Ion Mass Spectrometry to identify isotopically anomalous material in meteoritic IOM and IDPs at a ~100-200 nm scale. Organics of most likely interstellar origin are then extracted with the Focused-Ion-Beam technique and prepared for synchrotron X-ray and Transmission Electron Microscopy. These experiments yield information on the character of the H- and N-bearing interstellar molecules: While the association of H and N isotope anomalies with nanoglobules could be confirmed, we have also identified amorphous, micron-sized monolithic grains. D-enrichments in meteoritic IOM appear not to be systematically associated with any specific functional groups, whereas 15N-rich material can be related to imine and nitrile functionality. The large 15N- enrichments observed here (δ15N > 1000 ‰) cannot be reconciled with models using interstellar ammonia ice reactions, and hence, provide new constraints for understanding the chemistry in cold interstellar clouds.

We have studied the Raman spectroscopic signatures of nanodiamonds from the Allende meteorite in which some portions must be of presolar origin as indicated by the isotopic compositions of various trace elements. The spectra of the meteoritic nanodiamond show a narrow peak at 1326 cm−1 and a broad band at 1590 cm−1. Compared to the intensities of these peaks, the background fluorescence is relatively high. A significant frequency shift from 1332 to 1326 cm−1, peak broadening, and appearance of a new peak at 1590 cm−1 might be due to shock effects during formation of the diamond grains. Such changes may have several origins: an increase in bond length, a change in the electron density function or charge transfer, or a combination of these factors. However, Raman spectroscopy alone does not allow distinguishing between a shock origin of the nanodiamonds and formation by a CVD process as is favored by most workers.

Ultimately, all of the solids in the Solar System, including ourselves, consist of elements that were made in stars by stellar nucelosynthesis. However, most of the material from many different stellar sources that went into the making of the Solar System was thoroughly mixed, obliterating any information about its origin. An exception are tiny grains of preserved stardust found in primitive meteorites, micrometeorites, and interplanetary dust particles. These μm- and sub-μm-sized presolar grains are recognized as stardust by their isotopic compositions, which are completely different from those of the Solar System. They condensed in outflows from late-type stars and in SN ejecta and were included in meteorites, from which they can be isolated and studied for their isotopic compositions in the laboratory. Thus these grains constitute a link between us and our stellar ancestors. They provide new information on stellar evolution, nucleosynthesis, mixing processes in asymptotic giant branch (AGB) stars and supernovae, and galactic chemical evolution. Red giants, AGB stars, Type II supernovae, and possibly novae have been identified as stellar sources of the grains. Stardust phases identified so far include silicates, oxides such as corundum, spinel, and hibonite, graphite, silicon carbide, silicon nitride, titanium carbide, and Fe-Ni metal.

A small fraction of primitive meteorites and interplanetary dust particles (IDPs) consists of grains of presolar stardust. These grains have extremely unusual isotopic compositions, relative to all other planetary materials, indicating that they condensed in the outflows and explosions of prior generations of stars (Clayton & Nittler 2004). Identified presolar grain types include silicate, oxide and carbonaceous phases. The latter include graphitic carbon, diamond and SiC. Although many of these phases do not have a direct connection to organic chemistry, this is not true of the graphitic spherules. Many of these, with isotopic compositions indicating an origin in C-rich asymptotic giant branch (AGB) star outflows, have a structure consisting of naonocrystalline cores surrounded by well-graphitized C (Bernatowicz et al. 1996). The cores include isotopically anomalous polycyclic aromatic hydrocarbons (Messenger et al. 1998) and represent a link between molecular chemistry and dust condensation in stellar outflows. Meteorites and IDPs also contain abundant isotopically anomalous organic matter, including distinct organic grains, some of which probably formed in stellar outflows and/or the interstellar medium (ISM) (Busemann et al. 2006, Floss et al. 2004). In some IDPs, deuterium- and 15N-enriched organic matter is closely associated with presolar silicate grains (Messenger et al. 2005, Nguyen et al. 2007), suggesting an association in the ISM prior to Solar System formation.

The present work shows the proportion of interstellar meteors from different mass ranges (exceeding 20 orders of mass scale) detected by various observational techniques. Having analysed the IAU Meteor Data Center, we find that the mass index of interstellar particles continuously increases towards higher masses, but there is a significant change between 10−10 − 10−11 kg. This break is possibly caused by different physical processes leading to different populations of interstellar particles and might be connected with their origin.

If interstellar meteors are present among the registered meteor orbits, the distribution of the excesses of their heliocentric velocities should correspond to the distribution of radial velocities of close stars. Hence, for the velocity vi = 20 kms−1 of an interstellar meteor (with respect to the Sun) we obtain a heliocentric velocity vH = 46.6 kms−1 of an interstellar meteor arriving at the Earth. Moreover, a concentration of radiants to the Sun's apex should be observed. An analysis of the hyperbolic meteors among the 4581 photographic orbits of the IAU Meteor Data Center showed that the identification of the vast majority of the hyperbolic orbits in these catalogues has been caused by an erroneous determination of their heliocentric velocity and/or other parameters. Any error in the determination of vH, especially near the parabolic limit, can create an artificial hyperbolic orbit that does not really exist. On the basis of photographic meteors from the IAU MDC, the proportion of possible interstellar meteors decreased significantly (greater than 1 order of magnitude) after error analysis and does not exceed the value 2.5 × 10−4. Neither any concentration of radiants to the Sun's apex, nor any distribution following the motion of interstellar material has been found.

The possibility of an extraterrestrial origin of biomolecule building blocks has been a subject of intense discussions for many years. The detection of amino acids in meteorites opens the possibility of a delivery of biomolecules synthesized in the interstellar medium or star-forming regions to the primeval Earth. Whereas it can be doubted if more complex species like amino acids can survive the strong UV radiation in the early Solar System, this does not necessary hold for more primitive precursor molecules like nitriles. These compounds can also be synthesized very efficiently in methane-nitrogen dominated atmospheres like the one present on Titan and the early ages of Earth. This Contribution focuses on the formation and degradation processes of nitriles in interstellar clouds and planetary atmospheres and on their possible role in the generation of biomolecules.

Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of organic matter in space. Their contribution is invoked in a broad spectrum of astronomical observations that range from the ultraviolet to the far-infrared and cover a wide variety of objects and environments from meteorites and interplanetary dust particles to outer Solar System bodies to the interstellar medium in the local Milky Way and in other galaxies. Extensive efforts have been devoted in the past two decades to experimental, theoretical, and observational studies of PAHs. A brief review is given here of the evidence obtained so far for the contribution of PAHs to the phenomena aforementioned. An attempt is made to distinguish the cases where solid evidence is available from cases where reasonable assumptions can be made to the cases where the presence - or the absence - of PAHs is purely speculative at this point.

Aromatic Infrared Bands (AIBs) show significant profile variations in different astrophysical environments. Theoretical IR data is used to develop emission models to understand these variations. A good match with the observed “7.7” μm feature from different regions is obtained.

We present experimental results obtained from photoionization and photodissociation processes of abundant interstellar methanol (CH3OH) as an alternative route for the production of H3+ in dense clouds. The measurements were taken at the Brazilian Synchrotron Light Laboratory (LNLS) employing soft X-ray and time-of-flight mass spectrometry. Mass spectra were obtained using the photoelectron-photoion coincidence techniques. Absolute averaged cross sections for the production of H3+ due to molecular dissociation of methanol by soft X-rays (C1s edge) were determined. The H3+'s photoproduction rate and column density were been estimated adopting a typical soft X-ray luminosity inside dense molecular and the observed column density of methanol. Assuming a steady state scenario, the highest column density value for the photoproduced H3+ was about 1011 cm2, which gives the ratio photoproduced/observed of about 0.05%, as in the case of dense molecular cloud AFGL 2591. Despite the small value, this represent a new and alternative source of H3+ into dense molecular clouds and it is not been considered as yet in interstellar chemistry models.

We present experimental studies on the photoionization and photodissociation processes (photodestruction) of gaseous amino acids and nucleobases in interstellar and interpla-netary radiation analogs conditions. The measurements have been undertaken at the Brazilian Synchrotron Light Laboratory (LNLS), employing vacuum ultraviolet (VUV) and soft X-ray photons. The experimental set up basically consists of a time-of-flight mass spectrometer kept under high vacuum conditions. Mass spectra were obtained using a photoelectron photoion coincidence technique. We have shown that the amino acids are effectively more destroyed (up to 70–80%) by the stellar radiation than the nucleobases, mainly in the VUV. Since polycyclic aromatic hydrocarbons have the same survival capability and seem to be ubiquitous in the ISM, it is not unreasonable to predict that nucleobases could survive in the interstellar medium and/or in comets, even as a stable cation.

As the number of detections of complex molecules keeps increasing, answering the question about their formation becomes more pressing. Many of the saturated organic molecules are found to have a very low gas phase formation rate and are therefore thought to be formed on the icy surfaces of dust grains. In the Sackler Laboratory for Astrophysics we started a systematic study of the surface reaction routes that have been suggested over the years. Here we present the experimental results on the formation of methanol and ethanol by hydrogenation reactions of carbon monoxide and acetaldehyde ice. Computer simulations of the surface processes under similar conditions using the continuous-time random-walk Monte Carlo technique reveal some of the underlying physical processes. A better understanding of the physical conditions in which these molecules are formed can help in the interpretation of the observational results. The CO hydrogenation results will appear in detail in Fuchs et al. (2008). For more details on ethanol formation we refer to Bisschop et al. (2007).

New techniques for the generation and analysis of carbon nanoparticles (CNPs) have been developed and have resulted in the production of CNP samples whose infrared spectral properties are essentially identical to those observed in interstellar absorption and emission. These particles are of mixed aromatic/aliphatic composition. Spectra of CNPs containing 102–104 atoms will be discussed in relation to spectra of interstellar materials. We find that infrared line widths in these samples are typically 10–30 cm−1, but can be as small as 2 cm−1. Simulation of the 3.28 μm feature is shown to yield important new insight into the nature of interstellar CNPs.

Carbonaceous extraterrestrial matter is observed in a wide variety of astrophysical environments. The spectroscopic signatures revealed a large variety of chemical structure illustrating the rich carbon chemistry that occurs in space. In order to produce laboratory analogues of carbonaceous cosmic dust, a new chemical reactor has been built in the Laboratoire de Photophysique Moléculaire. It is a low pressure flat burner providing flames of premixed hydrocarbon / oxygen gas mixtures, closely following the model system used by the combustion community. In such a device the flame is a one-dimensional chemical reactor that offers a broad range of combustion conditions and sampling which allows production of many and various by-products. In the present work, we have studied: i) the infrared transmission spectra of thin film deposit samples whose nature ranges from strongly aromatic to strongly aliphatic materials; ii) the resonant two-photon photoionisation spectra of gas phase PAHs formed in the flame.

Our research has focused on the measurement of the electronic spectra of unstable molecules which are presumed to be of relevance to astrophysical observations. Among these are the carbon chains and their ions. Thus we have been using and developing a number of spectroscopic methods to determine their spectra in the gas phase, including absorption via cavity ring-down and REMPI methods. The species are produced in supersonic jets coupled with discharge and laser ablation sources. With the successful laboratory detection of the electronic spectra of a number of key species, such as bare carbon chains Cnn=4,5, comparisons with astrophysical data could be made which lead to interesting implications for the future search for the species which could be responsible for the diffuse interstellar bands. Among the recent relevant observations in the laboratory have been the electronic spectra of carbon rings, Cnn=14,18,22, the development of a method to study transitions in mass-selected ions collisionally relaxed to 20 K and held in a 22-pole radiofrequency trap, and the study of metal containing carbon chains.

When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500–900 K a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. Formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material.

Tholins are polymeric hydrogenated carbon nitrides formed from N2:CH4 mixtures exposed to electrical discharges. They are complex disordered solids, and their structural chemistry and formation processes are not yet fully understood. Tholins have been widely adopted as useful analogs of reddish organic solids associated with planetary bodies or in interstellar space (e.g., Titan's aerosols, reddish surfaces of outer objects, interstellar organics, etc.) for fitting astronomical observations. However, there has been little evidence to date that they in fact constitute pertinent model materials, i. e. with chemical structure/composition similar to those presumed to be present in planetary or interstellar organic solids. In this contribution, we first review recent advances made regarding the determination of composition and structure of tholins produced in the laboratory. They point to a high chemical selectivity in the range of functional groups present, the control of unsaturation by nitrogen, and the highly disordered character of the structures. In a second section, we discuss the relationship between chemistry and the optical properties of tholins, and we point out the lack of a unique relationship between the shape and strength of the visible absorption bands and the chemical composition or structure of the model tholins. The tholins exhibit similarities with HCN “polymers”, that are suspected to be present in cometary refractory dust. This points to the existence of possible similar polymerisation processes, and it suggests they could also be used as analogs of N-rich cometary organics. Laboratory-based studies of cometary dust might offer new insights on the “chemical relevancy” of tholins, as combined micro-analytical techniques will allow direct comparison of chemical information between the materials produced. In a third section we present recent results pertaining to the search for such compounds in cometary grains (Stardust grains, interplanetary dust particles - IDPs). We show that some N-rich spots in stratospheric IDPs are rich in cyanide species, but no tholin-like compounds or polymeric HCN have been detected to date.

Filmy-QCC is an organic material synthesized in the laboratory, and it exhibits red photoluminescence (PL). The peak wavelength of the PL ranges from 650 to 690 nm, depending on the mass distribution of polycyclic aromatic hydrocarbon (PAH) molecules, and the emission profile is a good match for that of the extended red emission in the Red Rectangle nebula. The quantum yield of the PL ranges from 0.009 to 0.04. When filmy-QCC is dissolved in cyclohexane, it exhibits blue PL in the wavelength range of 400–500 nm with a quantum yield of 0.12–0.16. The large width of the red PL and the large wavelength difference between the PL of the filmy-QCC as a solid film and in a solution indicate that there is a strong interaction between the components of filmy-QCC. The major components of filmy-QCC are PAHs up to 500 atomic mass units. Our laboratory data suggest that the blue luminescence observed in the Red Rectangle nebula is probably caused by small PAHs in a gaseous state, and the extended red emission is caused by larger PAHs in dust grains.

Carbonaceous materials have been prepared in the laboratory by laser-induced pyrolysis of a mixture of hydrocarbons under different conditions and laser ablation of graphite in reactive gas atmospheres. We have investigated the soluble and insoluble parts of the condensed carbon powders with several spectroscopic and chromatographic methods in order to obtain information on the composition of the condensate. The results of these experiments have demonstrated that, at temperatures lower than 1700 K, the pyrolysis by-products are mainly PAHs, whereas at higher temperatures fullerenes and polyyne-based compounds are formed. The experimental findings point to different soot formation mechanisms with variable intermediates and end products. It has been found that soot extracts can contain more than 65 different polycyclic aromatic hydrocarbons (PAHs). Eventually, the study of the condensation pathways of soot particles and their precursors and by-products will permit the prediction of the spectral properties of carbonaceous matter in space.

The thermal alteration process of filmy quenched carbonaceous composite (filmy QCC) has been studied in situ by high-resolution transmission electron microscopy (HRTEM). HRTEM images of the as-prepared filmy QCC showed the typical amorphous carbon film structure. By heating above 300 °C, the structural alteration takes place. Curled graphene structure started to appear at 300 °C. Distorted onion-like structure similar to dark QCC appeared above 500 to 700 °C. The distorted onion-like structure that appears at 700 °C after heating for 30 minutes also appeared by heating at 450 °C for 2 hours.